Vapor-permeable, substantially water-impermeable multilayer article

ABSTRACT

This disclosure relates to an article (e.g., a vapor-permeable, substantially water-impermeable multilayer article) that can include a nonwoven substrate and a film. supported by the nonwoven substrate. The film can include a polyolefin grafted with an anhydride, an acid, or an acrylate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent Application No. 61/500,206 filed Jun. 23, 2011, which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

This disclosure relates to vapor-permeable, substantially water-impermeable multilayer articles, as well as related products and methods.

BACKGROUND

Films that allow passage of gases at moderate to high transmission rates are often called breathable. The gases most commonly used to demonstrate a film's breathability are water vapor (also referred to herein as moisture vapor or moisture) and oxygen. The moisture and oxygen transmission tests measure the mass or volume of a gas transported across the cross-section of a film in a given unit of time at a defined set of environmental conditions. Breathable films can be classified as microporous films or monolithic films (which are not porous).

A breathable film can be laminated onto a nonwoven substrate to form a vapor-permeable, substantially water-impermeable multilayer article. A vapor-permeable, substantially water-impermeable multilayer article can refer to an article that allows the passage of a gas but substantially does not allow the passage of water.

SUMMARY

The inventors have unexpectedly discovered that a vapor-permeable, substantially water-impermeable multilayer article containing a modified polyolefin (e.g., a polyolefin grafted with an anhydride, an acid, or an acrylate) either in a monolithic breathable film or as an intermediate layer between a monolithic breathable film and a nonwoven substrate can have improved adhesion between the monolithic breathable film and the nonwoven substrate while maintaining or improving the moisture vapor transmission rate (MVTR) of the entire article. Such an article can be suitable for use as a construction material (e.g., a housewrap or a roofwrap).

In one aspect, this disclosure features an article that includes a nonwoven. substrate and a film supported by the nonwoven substrate. The film includes a first polymer containing a polyolefin grafted with an anhydride, art acid, or an acrylate,

In another aspect, this disclosure features an article that includes a nonwoven substrate, a first film supported by the nonwoven substrate, and a second film, The first film is between the nonwoven substrate and the second film and includes a first polymer containing a polyolefin grafted with an anhydride, an acid, or an acrylate. The second film includes a second polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids.

In still another aspect, this disclosure features a construction material (e.g., a housewrap or a roofwrap) that includes one of the articles described above.

Embodiments can include one or more of the following optional features.

The polyolefin in the first polymer can include a homopolymer or copolymer. For example, the polyolefin can include a polyethylene, a polypropylene, a poly(ethylene-co-vinyl acetate), or a polyethylene-co-acrylate).

The first polymer can include a low-density polyethylene grafted with an anhydride, a linear low-density polyethylene grafted with an anhydride, a high-density polyethylene grafted with an anhydride, a polypropylene grafted with an anhydride, a polyethylene-co-acrylate) grated with an anhydride or an acid, and a polyethylene-co-vinyl acetate) grafted with an anhydride, an acid, or an acrylate.

The film containing the first polymer can include from about 1% by weight to about 20% by weight of this polymer.

The film containing the first polymer can further include a second polymer (e.g., from about 30% by weight to about 70% by weight of the second polymer) capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids. The second polymer can be selected from the group consisting of maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof. Examples of the second polymer include poly(olefin-co-acrylate-co-maleic anhydride), poly(plefin-co-acrylate-co-glycidyl methacrylate), polyether ester block copolymers, polyether amide block copolymers, poly(ether ester amide) block copolymers, and polyurethanes.

The film containing the first polymer can further include a polyetheramine (e.g., from about 1% by weight to about 10% by weight of the polyetheramine).

The film containing the first polymer can further include a vinyl polymer (e.g., from about 20% by weight to about 80% by weight of the vinyl polymer). The vinyl polymer can include a copolymer formed between a first comonomer and a second comonomer, in which the first comonomer contains ethylene and the second commoner contains alkyl methacrylate, alkyl acrylate, or vinyl acetate. For example, the vinyl polymer can include a poly(ethylene-co-methyl acrylate), a poly(ethylene-co-vinyl acetate), a poly(ethylene-co-ethyl acrylate), or a poly(ethylene-co-butyl acrylate).

When the first film containing the first polymer is between a nonwoven substrate and a second film, the first film can include about 100% by weight of the first polymer. In such embodiments, the second film can include from about 20% by weight to about 100% by weight of the second polymer described above. The second film can further include the vinyl polymer described above (e.g., from about 20% by weight to about 80% by weight of the vinyl polymer).

The nonwoven substrate can include randomly disposed continuous polymeric fibers, at least some of the fibers being bonded to one another.

The article can have a moisture vapor transmission rate of at least about 5 perms (about 32 g/m²/day at 23° C. and 50% Relative Humidity (RH %)).

The article can have a hydrostatic head of at least about 55 cm.

The adhesion between the substrate and the film containing the first polymer can be at least about 50 gram-force/in.

The film containing the second polymer is a monolithic film.

Other features and advantages will be apparent from the description, drawings, and claims.

DESCRIPTION OF DRAWINGS

FIG. 1 is a cross-sectional view of an exemplary vapor-permeable, substantially water-impermeable bilayer article.

FIG. 2 is a cross-sectional view of an exemplary vapor-permeable, substantially water-impermeable trilayer article.

FIG. 3 is a scheme illustrating an exemplary extruding process. Like reference symbols in the various drawings indicate like elements.

DETAILED DESCRIPTION

This disclosure relates to, for instance, an article (e.g., a vapor-permeable, substantially water-impermeable multilayer article) containing a nonwoven substrate and a monolithic breathable film supported by the nonwoven substrate. In some embodiments, the monolithic breathable film can include a first polymer (e,g., a modified polyolefin) and a second polymer (e.g., a breathable polymer). In some embodiments, the article includes an intermediate layer containing the first polymer (e.g., a modified polyolefin) between the monolithic breathable film containing the second polymer (e.g., a breathable polymer) and the nonwoven substrate. The nonwoven substrate can be formed from polymeric fibers (e.g., fibers made from polyolefins)

Bilayer Article

FIG. 1 is a cross-sectional view of an exemplary vapor-permeable, substantially water-impermeable bilayer article 1 containing a monolithic breathable film 2 and a nonwoven substrate 4.

Monolithic Breathable Film 2

Film 2 can include a first polymer and a second polymer different from the first polymer.

In some embodiments, the first polymer includes a polyolefin grafted with an anhydride (e.g., an anhydride containing one to ten carbon atoms), an acid (e.g., a carboxylic acid containing one to ten carbon atoms), or an acrylate (e.g., an acrylate containing one to ten carbon atoms). The anhydride can be an acyclic anhydride (e.g., acetic anhydride) or a cyclic anhydride (e.g., maleic anhydride). The acrylate can be an alkyl acrylate (e,g., methyl acrylate, ethyl acrylate, or butyl acrylate) or an alkyl methacrylate (e.g., methyl methacrylate, ethyl methacrylate, or butyl methacrylate). The anhydride, acid, or acrylate can be grafted onto a side chain and/or a main chain of the first polymer.

As used here, the term “polyolefin” refers to a homopolymer or a copolymer made from at least a linear or branched, cyclic or acyclic olefin monomer. Examples of polyolefin homopolymers include polyethylene, polypropylene, polybutene, polypentene, and polymethylpentene. A polyolefin copolymer can be formed from an olefin monomer and one or more comonomers other than an olefins. Exemplary comonomers that can be used to make polyolefin copolymers include vinyl acetate or acrylates (e.g., alkyl acrylate such as methyl acrylate, ethyl acrylate, or butyl acrylate, or alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, or butyl methacrylate). Exemplary polyolefin copolymers include poly(ethylene-co-vinyl acetate)s and poly(ethylene-co-acrylate)s. In some embodiments, exemplary polyethylene homopolymers or copolymers include low-density polyethylene (e.g., having a density from 0.910 g/cm² to 0.925 g/cm²), linear low-density polyethylene (e.g., having a density from 0.910 g,/cm² to 0.935 g/cm²), and high-density polyethylene (e.g., having a density from 0.935 g/cm² to 0.970 g/cm²). High-density polyethylene can be produced by copolymerizing ethylene with one or more C₄ to C₂₀ α-olefin comonomers. Examples of suitable α-olefin comonomers include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and combinations thereof. The high-density polyethylene can include up to 20 mole percent of the above-mentioned α-olefin comonomers.

Examples of the first polymer include a low-density polyethylene grafted with an anhydride, a linear low-density polyethylene grafted with an anhydride, a high-density polyethylene grafted with an anhydride, a polypropylene grafted with an anhydride, a polyethylene-co-acrylate) grated with an anhydride or an acid, and a poly(ethylene-co-vinyl acetate) grafted with an anhydride, an acid, or an acrylate. Commercial examples of the first polymer include the BYNEL series of polymers available from E.I. du Pont de Nemours and Company, Inc. (Wilmington, Del.). In some embodiments, the BYNEL series of polymers have a relative low MVTR, such as less than about 5 perms (about 32 g/m²/day at 23° C. and 50 RH %).

In some embodiments, film 2 can include at least about 1% (e.g., at least about 2%, at least about 3%, at least about 5%, or at least about 10%) by weight and/or at most about 20% (e.g., at most about 18%, at most about 16%, at most about 14%, or at most about 12%) by weight of the first polymer. It is believed that the first polymer does not impart breathability to a film and therefore incorporating such a polymer into a film would reduce the breathability of the film. Unexpectedly, without wishing to be bound by theory, the inventors have discovered that film 2 containing the first polymer in the amount mentioned above can have improved adhesion or compatibility between film 2 and nonwoven substrate 4 while maintaining or even improving the MVTR of bilayer article 1.

The second polymer can be a breathable polymer. As used herein, “a breathable polymer” refers to a polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids (e.g., water). For example, a breathable polymer can absorb moisture from one side of film 2 and release it to the other side of film 2, thereby allowing the moisture to be transported through the film, As the breathable polymer can impart breathability to film 2, film 2 does not need to include pores. As such, film 2 can be monolithic and not porous.

In some embodiments, the breathable polymer in film 2 can include maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof. Examples of maleic anhydride block copolymers include poly(olefin-co-acrylate-co-maleic anhydride), such as poly(ethylene-co-acrylate-co-maleic anhydride). Commercial examples of maleic anhydride block copolymers include LOTADER MAH series of polymers available from Arkema (Philadelphia, Pa.) and. BYNEL series of polymers available from E.I. du Pont de Nemours and Company, Inc. Examples of glycidyl methacrylate block copolymers include poly(olefin-co-acrylate-co-glycidyl methacrylate), such as poly(ethylene-co-acrylate-co-glycidyl methacrylate). A commercial example of a glycidyl methacrylate block copolymer is LOTADER GMA series of polymers available from Arkema.

Examples of polyether block copolymers include polyether ester block copolymers, polyether amide block copolymers, and poly(ether ester amide) block copolymers. Commercial examples of polyether ester block copolymers include ARNITEL series of polymers available from DSM Engineering Plastics (Evansville, Ind.), HYTREL series of polymers available from E.I. du Pont de Nemours and Company, Inc., and NEOSTAR series of polymers available from Eastman Chemical Company (Kingsport, Tenn.). A commercial example of a polyether amide block copolymer is PEBAX series of polymers available from Arkema.

A polyethylene-containing ionomer can include an ethylene copolymer moiety and an acid copolymer moiety. The ethylene copolymer moiety can be formed by copolymerizing ethylene and a monomer selected from the group consisting of vinyl acetate, alkyl acrylate, and alkyl methacrylate. The acid copolymer moiety can be formed by copolymerizing ethylene and a monomer selected from the group consisting of acrylic acid and methacrylic acid. The acidic groups in the polyethylene-containing ionomer can be partially or fully converted to salts that include suitable cations, such as Li⁺, Na⁺K⁺, Mg⁺, and Zn²⁺. Examples of polyethylene-containing ionomers include those described in U.S. Patent Application Publication Nos. 2009/0142530 and 2009/0123689. Commercial examples of polyethylene-containing ionomers include ENTIRA and DPO AD 1099 series of polymers available from E.I. du Pont de Nemours and Company, Inc.

Other suitable breathable polymers have been described in, for example, U.S. Pat. Nos. 5,800,928 and 5,869,414.

The amount of the second polymer in film 2 can vary depending on the intended uses of article 1. In some embodiments, film 2 can include an amount of the second polymer that is sufficiently large to impart desired breathability to film 2 but sufficiently small to minimize manufacturing costs. For example, the second polymer can. be at least about 30% (e.g., at least about 35%, at least about 40%, at least about 45%, or at least about 50%) and/or at most about 70% (e.g., at most about 65%, at most about 60%, at most about 55%, at most about 50%, or at most about 45%) of the total weight of film 2.

As breathable polymers can be expensive to manufacture, film 2 can optionally include a vinyl polymer to reduce costs while maintaining the properties of this film. The vinyl polymer can include a copolymer formed between a first comonomer and a second comonomer different from the first comonomer. Examples of the first comonomer can be olefins (such as ethylene or propylene). Examples of the second commoner can include alkyl methacrylate (e.g., methyl methacrylate, ethyl methacrylate, or butyl methacrylate), alkyl acrylate (e.g., methyl acrylate, ethyl acrylate, or butyl acrylate), and vinyl acetate. Examples of suitable vinyl polymers include polyethylene-co-methyl acrylate), poly(ethylene-co-vinyl acetate), polyethylene-co-ethyl acrylate), and polyethylene-co-butyl acrylate). Commercial examples of the vinyl polymer include the LOTRYL series of polymers available from Arkema.

In some embodiments, film 2 can include at least about 20% (e.g., at least about 25%, at least about 30%, at least about 35%, at least about 40%, or at least about 50%) and/or at most about 80% (e.g., at most about 75%, at most about 70%, at most about 65%, at most about 60%, or at most about 55%) by weight of the vinyl polymer.

In some embodiments, film 2 can optionally include a polar compound, such as a polyetheramine. A commercial example of a polyetheramine is Elastamine series of polymers available from Huntsman Performance Products (The Woodlands, Tex.). In some embodiments, film 2 can include at least about 1% (e.g., at least about 2%, at least about 3%, at least about 4%, or at least about 5%) by weight and/or at most about 10% (e.g., at most about 9%, at most about 8%, at most about 7%, at most about 6%, or at most about 5%) by weight of the polyetheramine. Without wishing to be bound by theory, it is believed that incorporating the polar compound in film 2 can facilitate the transport of moisture through the film and thereby increase the MVTR of the film.

In some embodiments, the polar compound and the first polymer can be included in one composition before they are mixed with the other components used to form film 2. A commercial example of such a composition is PM14607 available from Techmer PM (Knoxville, Tenn.), which can include about 70% by weight of the first polymer and about 30% by weight of the polar compound.

In some embodiments, at least a portion (e.g., all) of the polar compound can react with and be grafted onto the first polymer. In such embodiments, the first polymer can include the polar groups (e.g., the amine groups) on the polar compound. Without wishing to be bound by theory, it is believed that such a first polymer can both improve the adhesion between film 2 and nonwoven substrate 4 and improve the MVTR of bilayer article 1.

In some embodiments, film 2 can have a thickness of at least about 5 μm (e.g., at is least about 10 μm, at least about 15 μm, or at least about 20 μm) and/or at most about 50 μm (e.g., at most about 45 μm, at most about 40 μm, or at most about 35 μm).

Nonwoven Substrate 4

Nonwoven substrate 4 can include randomly disposed polymeric fibers, at least some of the fibers being bonded to one another. As used herein, the term “nonwoven substrate” refers to a substrate containing one or more layers of fibers that are bonded together, but not in an identifiable manner as in a knitted or woven material.

Nonwoven substrate 4 can be formed from any suitable polymers. Exemplary polymers that can be used to form nonwoven substrate 4 include polyolefins and polyesters. Examples of suitable polyolefins include polyethylene, polypropylene, and copolymers thereof, such as those used in the first polymer in film 2 described above. Examples of suitable polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyglycolide or polyglycolic acid (PGA), polylactide or polylactic acid (PLA), polycaprolactone (PCL), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), and copolymers thereof.

Nonwoven substrate 4 can be formed from single component fibers, i.e., fibers containing a polymer having a single chemical structure (e.g., a polymer described in the preceding paragraph such as a polyethylene, a polypropylene, a polyethylene terephthalate, or a copolymer thereof). In some embodiments, nonwoven substrate 4 can include single component fibers made from polymers having the same chemical structure but different characteristics (e.g., molecular weights, molecular weight distributions, density, or intrinsic viscosities). For example, substrate 4 can include a mixture of a low-density polyethylene and a high-density polyethylene. Such fibers are still referred to as single component fibers in this disclosure.

Nonwoven substrate 4 can also be formed from multicomponent fibers, i.e., fibers containing polymers with different chemical structures (such as two different polymers described above). For example, substrate 4 can be formed from a mixture of a is polypropylene and a polyethylene terephthalate. In some embodiments, a multicomponent fiber can have a sheath-core configuration (e.g., having a polyethylene terephthalate as the core and a polypropylene as the sheath). In some embodiments, a multicomponent fiber can include two or more polymer domains in a configuration (e.g., a side-by-side configuration, a pie configuration, or an “islands-in-the-sea” configuration) different from the sheath-core configuration.

In some embodiments, the surface of nonwoven substrate 4 can be formed of a polymer having a chemical structure similar to (e.g., the same type as) or the same as the chemical structure of a polymer in the surface of film 2. As an example, a polyolefin (e.g., a polyethylene or propylene) is the same type as and similar to a different polyolefin (e.g., a polyethylene or propylene). Without wishing to be bound by theory, it is believed that such two layers can have improved adhesion. For example, when nonwoven substrate 4 is formed from single component fibers, the fibers can be made from a polyolefin, which has a chemical structure similar to the first polymer in film 2. When nonwoven substrate 4 is formed of multicomponent fibers (e.g., having a sheath-core configuration), the polymer (e.g., a polyolefin in the sheath) in the fibers that contacts film 2 can have a chemical structure similar to that of the first polymer in film 2. Both examples described above can result in a multilayer article with improved adhesion between the film and the nonwoven substrate.

Nonwoven substrate 4 can be made by methods well known in the art, such as a spunlacing, spunbonding, meltblowing, carding, air-through bonding, or calendar bonding process.

In some embodiments, nonwoven substrate 4 can be a spunbonded nonwoven substrate. In such embodiments, nonwoven substrate 4 can include a plurality of random continuous fibers, at least some (e.g., all) of which are bonded (e,g., area bonded or point bonded) with each other through a plurality of intermittent bonds. The term “continuous fiber” mentioned herein refers to a fiber formed in a continuous process and is not shortened before it is incorporated into a nonwoven substrate containing the continuous fibers.

As an example, nonwoven substrate 4 containing single component fibers can be made by using a spunbonding process as follows.

After the polymer for making single component fibers is melted, the molten polymer can be extruded from an extruding device. The molten polymer can then be directed into a spinneret with composite spinning orifices and spun through this spinneret to form continuous fibers. The fibers can subsequently be quenched (e.g., by cool air), attenuated mechanically or pneumatically (e.g., by a high velocity fluid), and collected in a random arrangement on a surface of a collector (e.g., a moving substrate such as a moving wire or belt) to form a nonwoven web. In some embodiments, a plurality of spinnerets with different quenching and attenuating capability can be used to place one or more (e.g., two, three, four, or five) layers of fibers on a collector to form a substrate containing one or more layers of spunbonded (S) fibers (e.g., an S, SS, or SSS type of substrate). In some embodiments, one or more layers of meltblown (M) fibers can be inserted between the layers of the above-described spunbonded fibers to form a substrate containing both spunbonded and meltblown fibers (e.g., an SMS, SMMS, or SSMMS type of substrate).

A plurality of intermittent bonds can subsequently be formed between at least some of the fibers (e,g., all of the fibers) randomly disposed on the collector to form a unitary, coherent, nonwoven substrate. Intermittent bonds can be formed by a suitable method such as mechanical needling, thermal bonding, ultrasonic bonding, or chemical bonding. Bonds can be covalent bonds (e.g., formed by chemical bonding) or physical attachments (e.g., formed by thermal bonding). In some embodiments, intermittent bonds are formed by thermal bonding. For example, bonds can be formed by known thermal bonding techniques, such as point bonding (e.g., using calender rolls with a point bonding pattern) or area bonding (e.g., using smooth calender rolls without any pattern). Bonds can cover between about 6 percent and about 40 percent (e.g., between about 8 percent and about 30 percent or between about 22 percent and about 28 percent) of the total area of nonwoven substrate 4. Without wishing to be bound by theory, it is believed that forming bonds in substrate 4 within these percentage ranges allows elongation throughout the entire area of substrate 4 upon stretching while maintaining the strength and integrity of the substrate.

Optionally, the fibers in nonwoven substrate 4 can be treated with a surface-modifying composition after intermittent bonds are formed. Methods of applying a surface-modifying composition to the fibers have been described, for example, in U.S. Provisional Patent Application No. 61/294,328.

Nonwoven substrate 4 thus formed can then be used to form bilayer article 1 described above. A nonwoven substrate containing multicomponent fibers can be made in a manner similar to that described above. Other examples of methods of making a nonwoven substrate containing multicomponent fibers have been described in, for example, U.S. Provisional Patent Application No. 61/294,328.

Trilayer Article

FIG. 2 is a cross-sectional view of an exemplary vapor-permeable, substantially water-impermeable trilayer article 10 containing a monolithic breathable film 12, an intermediate film 16, and a nonwoven substrate 14.

Intermediate film 16 can include the first polymer described in connection with bilayer article 1 above (i.e., a polyolefin grafted with an anhydride, an acid, or an acrylate). In such embodiments, intermediate layer 16 can be made substantially from the first polymer (i.e., containing about 100% of the first polymer).

In some embodiments, intermediate film 16 can have a thickness of at least about 0.2 μm (e.g., at least about 0.4 μm, at least about 0.6 μm, at least about 0.8 μm, or at least about 1 μm) and/or at most about 5 μm (e.g., at most about 4 μm, at most about 3 μm, at most about 2 μm, or at most about 1 μm). It is believed that a film containing the first polymer is not breathable and therefore incorporating such a polymer as an intermediate layer between a breathable film and a nonwoven substrate can reduce the breathability of the article. Without wishing to be bound by theory, the inventors have discovered that intermediate film 16 having a thickness mentioned above can improve the adhesion between film 12 and nonwoven substrate 14 while still maintaining the MVTR of trilayer article 10 at an acceptable level.

Monolithic breathable film 12 can include the second polymer described in connection with bilayer article 1 above (i.e., a breathable polymer), in some embodiments, the second polymer can be at least about 20% (e.g., at least about 30%, at least about 40%, at least about 50%, or at least about 60%) and/or at most about 100% (e.g., at most about 90%, at most about 80%, at most about 70%, at most about 60%, or at most about 50%) of the total weight of film 12.

In some embodiments, monolithic breathable film 12 can optionally include the vinyl polymer described in connection with bilayer article 1 above. In some embodiments, film 12 can include at least about 20% (e.g., at least about 25%, at least about 30%, at least about 35%, at least about 40%, or at least about 50%) and/or at most about 80% (e.g., at most about 75%, at most about 70%, at most about 65%, at most about 60%, or at most about 55%) by weight of the vinyl polymer.

In some embodiments, monolithic breathable film 12 can have a thickness of at least about 10 μm (e.g., at least about 12 μm, at least about 14 μm, at least about 16 μm, at least about 18 μm, or at least about 20 μm) and/or at most about 30 μm (e.g., at most about 28 μm, at most about 26 μm, at most about 24 μm, at most about 22 μm, or at most about 20 μm). In some embodiments, the ratio between the thickness of film 12 and the thickness of intermediate film 16 can be at most about 150:1 (e.g., at most about 100:1, at most about 50:1, at most about 20:1, or at most about 10:1) and/or at least about 2:1 (e.g., at least about 5:1, at least about 10:1, at least about 15:1, or at least about 20:1).

Nonwoven substrate 14 can be the same or have the same characteristics as nonwoven substrate 4 described in connection with bilayer article 1 above.

Method of Making Multilayer Article 1 or 10

Multilayer article 1 or 10 can be made by the methods known in the art or the methods described herein. An exemplary method of making trilayer article 10 is described below. Bilayer article 1 can be made in a similar manner except that the nonwoven substrate is coated with only one layer, instead of two layers.

In some embodiments, trilayer article 10 can be made by applying films 12 and 16 onto nonwoven substrate 14. Films 12 and 16 can be applied onto nonwoven substrate 14 by co-extruding (e.g., cast extrusion) a suitable composition for film 12 (e.g., a composition containing the second polymer) and a suitable composition for film 16 (e.g., a composition containing the first polymer) at an elevated temperature to form two layers onto nonwoven substrate 14. In some embodiments, the just-mentioned compositions can be co-extruded (e.g., by tubular extrusion or cast extrusion) to form a web, which can be cooled (e.g., by passing through a pair of rollers) to form a precursor two-layer structure. Trilayer article 10 can then be formed by attaching the precursor structure to nonwoven substrate 14 by using, for example, an adhesive (e.g., a spray adhesive, a hot melt adhesive, or a latex based adhesive), thermal bonding, ultra-sonic bonding, or needle punching.

FIG. 3 is a scheme illustrating an exemplary process for making trilayer article 10 described above. As shown in FIG. 3, a suitable composition for film 16 (e.g., a composition containing the first polymer) can be fed into an inlet 26 of an extruder hopper 24. The composition can then be melted and mixed in a screw extruder 20. The molten mixture can be discharged from extruder 20 under pressure through a heated line 22 to a flat film die 38. A suitable composition for film 12 (e.g., a composition containing a breathable polymer) can be fed into an inlet 36 of an extruder hopper 34. The composition can then be melted and mixed in a screw extruder 30. The molten mixture can be discharged from extruder 30 under pressure through a heated line 32 to flat film die 38 to be co-extruded with the molten mixture for film 16. Co-extruded melt 40 discharging from fiat film die 38 can be coated on nonwoven substrate 14 supplied from roll 50 such that film 16 is between nonwoven substrate 14 and film 12. The coated substrate can then enter a nip formed between rolls 52 and 56, which can be maintained at a suitable temperature (e.g., between about 10-120° C.). Passing the coated substrate through the nip formed between cooled rolls 52 and 56 can quench co-extrusion melt 40 while at the same time compressing co-extrusion melt 40 so that it forms a contact on nonwoven substrate 14. In some embodiments, roll 52 can be a smooth rubber roller with a low-stick surface coating while roll 56 can be a metal roll. A textured embossing roll can be used to replace metal roll 56 if a multilayer article with a textured film layer is desired. When co-extrusion melt 40 is cooled, it forms films 16 and 12 laminated onto nonwoven substrate 14. The laminate thus formed can then be collected on a collection roll 54 to form trilayer article 10. In some embodiments, the surface of nonwoven substrate 14 can be corona or plasma treated before it is coated with co-extrusion melt 40 to improve the adhesion between nonwoven substrate 14 and films 16 and 12.

In some embodiments, trilayer article 10 formed above can be embossed (e.g., by using a calendaring process). For example, trilayer article 10 can be embossed by passing through a pair of calender rolls in which one roll has an embossed surface and the other roll has a smooth surface. Without wishing to be bound by theory, it is believed that an embossed multilayer article can have a large surface area, which can facilitate vapor transmission through the multilayer article. In some embodiments, at least one (e.g., both) of the calender rolls is heated, e.g., by circulating a hot oil through the roll, during the embossing process.

Properties of Multilayer Article 1 or 10

In some embodiments, multilayer article 1 or 10 can have a suitable MVTR based on its intended uses. As used herein, the MVTR values are measured according to ASTM to E96 A. For example, multilayer article 1 or 10 can have a MVTR of at least about 5 perms (about 32 g/m²/day when measured at and 50 RH %) (e.g., at least about 6 perms (about 39 g/m²/day at 23° C. and 50 RH %), at least about 8 perms (about 52 g/m²/day at 23° C. and 50 RH %), or at least about 10 perms (about 65 g/m²/day at 23° C. and 50 RH %)) and/or at most about 20 perms (about 130 g/m²/day when measured at is 23° C. and 50 RH %) (e.g., at most about 17 perms (about 110 g/m²/day at 23° C. and 50 RH %), at most about 15 perms (about 97 g/m²/day at 23° C. and 50 RH %), or at most about 12 perms (about 77 g/m²/day at 23° C. and 50 RH %)). For instance, multilayer article 10 can have a MVTR of between 8 perms (about 52 g/m²/day at 23° C. and 50 RH %) and 15 perms (about 97 g/m²/day at 23° C. and 50 RH %).

In some embodiments, multilayer article 1 or 10 can have a sufficient tensile strength in the machine direction and/or the cross-machine direction. The tensile strength is determined by measuring the tensile force required to rupture a sample of a sheet material. The tensile strength mentioned herein is measured according to ASTM D5034 and is reported in pounds. In some embodiments, multilayer article 1 or 10 can have a tensile strength of at least about 40 pounds (e.g., at least about 50 pounds, at least about 60 pounds, at least about 70 pounds, or at least about 80 pounds) and/or at most about 160 pounds (e.g., at most about 150 pounds, at most about 140 pounds, at most about 130 pounds, or at most about 120 pounds) in the machine direction. In some embodiments, multilayer article 1 or 10 can have a tensile strength of at least about 35 pounds (e.g., at least about 40 pounds, at least about 50 pounds, at least about 60 pounds, or at least about 70 pounds) and/or at most about 140 pounds (e.g., at most about 130 pounds, at most about 120 pounds, at most about 110 pounds, or at most about 100 pounds) in the cross-machine direction.

As a specific example, when multilayer article 1 or 10 has a unit weight of 1.25 ounce per square yard (osy), it can have a tensile strength of at least about 40 pounds (e.g., at least about 45 pounds, at least about 50 pounds, at least about 55 pounds, or at least about 60 pounds) and/or at most about 100 pounds (e.g., at most about 95 pounds, at most about 90 pounds, at most about 85 pounds, or at most about 80 pounds) in the machine direction, and at least about 35 pounds (e.g., at least about 40 pounds, at least about 45 pounds, at least about 50 pounds, or at least about 55 pounds) and/or at most about 95 pounds (e.g., at most about 90 pounds, at most about 85 pounds, at most about 80 pounds, or at most about 75 pounds) in the cross-machine direction.

In some embodiments, multilayer article 1 or 10 can have a sufficient elongation in the machine direction and/or the cross-machine direction. Elongation is a measure of the amount that a sample of a sheet material will stretch under tension before the sheet breaks. The term “elongation” used herein refers to the difference between the length just prior to breaking and the original sample length, and is expressed as a percentage of the original sample length. The elongation values mentioned herein are measured according to ASTM D5034. For example, multilayer article 1 or 10 can have an elongation of at least about 5% (e.g., at least about 10%, at least about 20%, at least about 30%, at least about 35%, or at least about 40%) and/or at most about 100% (e.g., at most 90%, at most about 80%, or at most about 70%) in the machine direction. As another example, multilayer article 1 or 10 can have an elongation of at least about 5% (e.g., at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50%) and/or at most about 100% (e.g., at most about 90%, at most about 80%, or at most about 70%) in the cross-machine direction.

In some embodiments, multilayer article 1 or 10 can have a sufficient hydrostatic head value so as to maintain sufficient water impermeability. As used herein, the term “hydrostatic head” refers to the pressure of a column of water as measured by its height that is required to penetrate a given material and is determined according to AATCC 127. For example, multilayer article 1 or 10 can have a hydrostatic head of at least about 55 cm (e.g., at least about 60 cm, at least about 70 cm, at least about 80 cm, at least about 90 cm, or at least about 100 cm) and/or at most about 900 cm (e.g., at most about 800 cm, at most about 600 cm, at most about 400 cm, or at most about 200 cm.).

Without wishing to be bound by theory, it is believed that, in trilayer article 10, the adhesion between film 16 and nonwoven substrate 14 is significantly higher than that between film 12 and nonwoven substrate. For example, the adhesion between film 16 and nonwoven substrate 14 can be at least about 50 gram-force/in. (e.g., at least about 100 gram-force/in, at least about 200 gram-force/in, at least about 300 gram-force/in, at least about 500 gram-force/in, at least about 1,000 gram-force/in, or at least about 1,500 gram-force/in). By contrast, the adhesion between film 12 and nonwoven substrate 14 can be, in some embodiments, at most about 200 gram-force/in (e.g., at most about 150 gram-force/in, at most about 100 gram-force/in, at most about 50 gram-force/in, or at most about 10 gram-force/in). As a result, film 16 can improve the adhesion between nonwoven substrate 14 and film 12.

Multilayer article 1 or 10 can be used in a consumer product with or without further modifications. Examples of such consumer products include construction materials, such as a housewrap or a roofwrap. Other examples include diapers, adult incontinence devices, feminine hygiene products, medical and surgical gowns, medical drapes, and industrial apparels.

While certain embodiments have been disclosed, other embodiments are also possible.

In some embodiments, an effective amount of various additives can be incorporated in a film or the nonwoven substrate in multilayer article 1 or 10. Suitable additives include pigments, antistatic agents, antioxidants, ultraviolet light stabilizers, antiblocking agents, lubricants, processing aids, waxes, coupling agents for fillers, softening agents, thermal stabilizers, tackifiers, polymeric modifiers, hydrophobic compounds, hydrophilic compounds, anticorrosive agents, and mixtures thereof. In certain embodiments, additives such as polysiloxane fluids and fatty acid amides can be included to improve processability characteristics.

Pigments of various colors can be added to multilayer article 1 or 10 so that the resultant article is substantially opaque and exhibits uniform color. For example, multilayer article 1 or 10 can have a sufficient amount of pigments to produce an opacity of at least about 85% (e.g., at least about 90%, at least about 95%, at least about 98%, or4 at least about 99%). Suitable pigments include, but are not limited to, antimony trioxide, azurite, barium borate, barium sulfate, cadmium pigments (e.g., cadmium sulfide), calcium chromate, calcium carbonate, carbon black, chromium(III) oxide, cobalt pigments (e.g., cobalt(II) aluminate), lead tetroxide, lead(II) chromate, lithopone, orpiment, titanium dioxide, zinc oxide and zinc phosphate. Preferably, the pigment is titanium dioxide, carbon black, or calcium carbonate. The pigment can be about 1 percent to about 20 percent (e.g., about 3 percent to about 10 percent) of the total weight of a film or the nonwoven substrate in multilayer article 1 or 10. Alternatively, the pigment can be omitted to provide a substantially transparent multilayer article.

In some embodiments, certain additives can be used to facilitate manufacture of multilayer article 1 or 10. For example, antistatic agents can be incorporated into a film or the nonwoven substrate to facilitate processing of these materials. In addition, certain additives can be incorporated in multilayer article 1 or 10 for specific end applications.

For example, anticorrosive additives can be added if multilayer article 1 or 10 is to be used to package items that are subject to oxidation or corrosion. As another example, metal powders can be added to provide static or electrical discharge for sensitive electronic components such as printed circuit boards.

Each film and the nonwoven substrate in multilayer article 1 or 10 can also include a filler. The term “filler” can include non-reinforcing, fillers, reinforcing fillers, organic fillers, and inorganic fillers. For example, the filler can be an inorganic filler such as talc, silica, clays, solid flame retardants, Kaolin, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, alumina, mica, glass powder, ferrous hydroxide, zeolite, barium sulfate, or other mineral fillers or mixtures thereof. Other fillers can include acetyl salicylic acid, ion exchange resins, wood pulp, pulp powder, borax, alkaline earth metals, or mixtures thereof. The filler can be added in an amount of up to about 60 weight percent (e.g., from about 2 to about 50 weight percent) of a film or the nonwoven substrate in multilayer article 1 or 10.

In some embodiments, the surface of a film or the nonwoven substrate in multilayer article 1 or 10 can be at least partially treated to promote adhesion. For example, the surface can be corona charged or flame treated to partially oxidize the surface and enhance surface adhesion. Without wishing to be bound by theory, it is believed that multilayer article 1 or 10 having enhanced surface adhesion can enable printing on its surface using conventional inks. Ink-jet receptive coating can also be added to the surface of multilayer article 1 or 10 to allow printing by home or commercial inkjet printers using water based or solvent based inks.

In some embodiments, a multilayer article described herein can include multiple (e.g., two, three, four, or five) films supported by nonwoven substrate 14, at least two of the films are films 12 and 16 described in FIG. 2 above. The additional films can be made by one or more of the materials used to prepare film 12 or 16 described above or other materials known in the art. In some embodiments, nonwoven substrate 14 can be disposed between two of the multiple films. In some embodiments, all of the films can be disposed on one side of nonwoven substrate 14.

The following examples are illustrative and not intended to be limiting.

EXAMPLE 1

The following four bilayer articles were prepared: (1) TYPAL (i.e., a polypropylene spunbonded nonwoven substrate available from Fiberweb, Inc) having a unit weight of 1.9 ounce per square inch and coated with a monolithic breathable film containing 40 wt % PEBAX MV3000, 51 wt % LOTRYL 20MA08 (i.e., an ethyl methacrylate), 5 wt % BYNEL 22E757, 2 wt % TiO₂ (10SAM0242 available from Standridge Color Corporation (Social Circle, Ga.)), and 2 wt % UV stabilizer (10743-08 available from Colortech Inc. (Morristown, Tenn.)); and (2) a bilayer article similar to Mayer article (1) except that the monolithic breathable film included 40 wt % PEBAX MV3000, 46 wt % LOTRYL 20MA08, 5 wt % PM14607 which included 70 wt % BYNEL 22E757 and 30 wt % Elastamine), 5 wt % BYNEL 22E757, 2 wt % TiO₂, and 2 wt % UV stabilizer; (3) a bilayer article similar to bilayer article (1) except that the monolithic breathable film included 40 wt % PEBAX MV3000, 41 wt % LOTRYL 20MA08, 1.0 wt % PM14607, 5 wt % BYNEL 22E757, 2 wt % TiO₂, and 2 wt % UV stabilizer; and (4) a Mayer article similar to bilayer article (1) except that the monolithic breathable film included 40 wt % PEBAX MV3000, 36 wt % LOTRYL 20MA08, 15 wt % PM14607, 5 wt % BYNEL 22E757, 2 wt % TiO₂, and 2 wt % UV stabilizer. The bilayer articles were formed by extruding the monolithic breathable film onto TYPAR at 520° F.

Bilayer articles (1)-(4) were evaluated for their MVTR, hydrostatic head, and adhesion properties. The adhesion was measured as follows: 9-inch long samples were prepared by adhering a 2-inch wide housewrap tape over the coating (folding over one end of the tape onto itself to provide a tab for gripping) to prevent elongation of the coating. The peel adhesion of the samples was then measured by using an Instron or IMASS peel tester with a 5-pound load cell. A 180 degree peel angel was used with a rate of separation of 12 in/minute. The test results are summarized in Table 1 below.

TABLE 1 Film Weight MVTR Hydrostatic (gsm) Substrate (Perm) head (cm) Article (1) 20 TYPAR 1.9 8 536 Article (2) osy 8.5 712 Article (3) (10 den) 9.1 412 Article (4) 14.1 51

As articles (2)-(4) had higher amounts of BYNEL (i.e., a breathable polymer with a relatively low MVTR) than article (1), one would expect that they would exhibit lower breathablility than article (1). Unexpectedly, the results in Table 1 showed that, with an increasing amount of Elastamine, articles (2)-(4) exhibited an increasing MVTR even though they contained an increasing amount of BYNEL.

EXAMPLE 2

The following three multilayer articles were prepared: (1) a bilayer article containing TYPAR having a unit weight of 1.9 ounce per square inch and coated with a monolithic breathable film containing 70 wt % NEOSTAR FN005, 26 wt % LOTRYL 20MA08 (i.e., an ethyl methacrylate), 2 wt % TiO₂ (10SAM0242), and 2 wt % UV stabilizer (10743-08); and (2) a trilayer article having the same TYPAR substrate and the monolithic breathable film as bilayer article (1), but further including an intermediate film containing 100 wt % BYNEL 22E757 between the monolithic breathable film and TYPAR; and (3) a trilayer article similar to trilayer article (2) except that the monolithic breathable film included 96 wt % NEOSTAR FNOOS, 2 wt % TiO₂ (10SAM0242), and 2 wt % UV stabilizer (10743-08). In articles (2) and (3), the ratio of the thickness between the monolithic breathable film and the intermediate film was about 4:1. In addition, the total weight of the films in articles (2) and (3) were 18 gsm, while the weight of the film in article (1) was 28 gsm.

Bilayer article (1) was formed by extruding the monolithic breathable fill a onto TYPAR at 480° F. Trilayer articles (2) and (3) were formed by co-extruding the monolithic breathable film and the intermediate film onto TYPAR. The extruder temperatures for the monolithic breathable film and the intermediate film were 480° F. and 520° F., respectively.

Multilayer articles (1)-(3) were evaluated for their MVTR, hydrostatic head, and adhesion properties between the TYPAR and the intermediate film. The test results are summarized in Table 2 below.

TABLE 2 Film Weight MVTR Hydrostatic Adhesion (gsm) Substrate (Perm) head (cm) (gram-force/in) Article (1) 28 TYPAR 11 713 <20 Article (2) 18 1.9 osy 14 283 100 Article (3) 18 (10 den) 15.3 528 57

As articles (2) and (3) had a smaller film weight and therefore a smaller film thickness than article (1), one would expect that they would exhibit lower adhesion between the films and the TYPAR substrate. Unexpectedly, the results showed that articles (2) and (3) (each of which included an intermediate film) exhibited significantly higher adhesion between the films and the TYPAR substrate than that found in article (1). Further, at a reduced film weight, articles (2) and (3) exhibited an improved MVTR compared to article (1).

EXAMPLE 3

The following three multilayer articles were prepared: (1) a bilayer article containing TYPAR having a unit weight of 1.9 ounce per square inch and coated with a monolithic breathable film containing 100 wt % ENTIRA AD1099; and (2) a trilayer is article having the same TYPAR substrate and the monolithic breathable film as bilayer article (1), but further including an intermediate film containing 100 wt % BYNEL E418 between the monolithic breathable film and TYPAR, the total weight of the films in article (2) being 30 gsm; and (3) a trilayer article similar to trilayer article (2) except that the total weight of the films in article (3) was 25 gsm. In articles (2) and (3), the thickness of the monolithic breathable film and the intermediate film was 25 μm and 2 μm, respectively.

Bilayer article (1) was formed by extruding the monolithic breathable film onto TYPAR at 455° F. Trilayer articles (2) and (3) were formed by co-extruding the monolithic breathable film and the intermediate film onto TYPAR. The extruder temperatures for the monolithic breathable film and the intermediate film were 455° F. and 520° F., respectively.

Multilayer articles (1)-(3) were evaluated for their MVTR, hydrostatic head, and adhesion properties. The adhesion was measured by using the same method described in Example 2. The test results are summarized in Table 3 below.

TABLE 3 Film Weight MVTR Hydrostatic Adhesion (gsm) Substrate (Perm) head (cm) (gram-force/in) Article (1) 25 TYPAR 15 825 <30 Article (2) 30 1.9 osy 6.2 847 >250 Article (3) 25 (10 den) 9.5 765 >250

The results showed that articles (2) and (3) (each of which included an intermediate film) exhibited significantly higher adhesion between the films and the TYPAR substrate. Further, at the same film weight as that of article (1), article (3) unexpectedly exhibited an acceptable MVTR even though it included an intermediate film containing a polymer with a relatively low MVTR.

Other embodiments are in the claims. 

1-45. (canceled)
 46. A method of forming a multilayer article, comprising: applying a first film layer onto a nonwoven substrate; wherein the first film layer comprises (i) a first polymer comprising a polyolefin grafted with an anhydride, an acid, or an acrylate; (ii) a second polymer that is different from the first polymer and comprising from 30% by weight to 35% by weight of the first film layer, the second polymer comprising a breathable polymer being capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids, and (iii) from at least about 1% by weight to at most about 10% by weight of a polar compound.
 47. The method of claim 46, wherein applying the first film comprises extrusion coating the first film onto the nonwoven substrate.
 48. The method of claim 46, wherein the polar compound comprises a polyetheramine.
 49. The method of claim 46, wherein the first film is a monolithic film.
 50. The method of claim 46, wherein the polyolefin comprises a homopolymer or copolymer.
 51. The method of claim 46, wherein the polyolefin comprises a polyethylene, a polypropylene, a poly(ethylene-co-vinyl acetate), or a poly(ethylene-co-acrylate).
 52. The method of claim 46, wherein the first polymer comprises a low-density polyethylene grafted with an anhydride, a linear low-density polyethylene grafted with an anhydride, a high-density polyethylene grafted with an anhydride, a polypropylene grafted with an anhydride, a poly(ethylene-co-acrylate) grated with an anhydride or an acid, and a poly(ethylene-co-vinyl acetate) grafted with an anhydride, an acid, or an acrylate.
 53. The method of claim 46, wherein the first film comprises from about 1% by weight to about 20% by weight of the first polymer.
 54. The method of claim 46, wherein the second polymer is selected from the group consisting of maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof.
 55. The method of claim 46, wherein the second polymer is selected from the group consisting of poly(olefin-co-acrylate-co-maleic anhydride), poly(olefin-co-acrylate-co-glycidyl methacrylate), polyether ester block copolymers, polyether amide block copolymers, poly(ether ester amide) block copolymers, and polyurethanes.
 56. The method of claim 46, wherein the second polymer is selected from the group consisting of polyether ester block copolymers, poly(ethylene-co-acrylate-co-maleic anhydride), and poly(ethylene-co-acrylate-co-glycidyl methacrylate).
 57. The method of claim 46, wherein the first film further comprises a vinyl polymer.
 58. The method of claim 57, wherein the first film comprises from about 20% by weight to about 50% by weight of the vinyl polymer.
 59. The method of claim 46, further comprising embossing the multilayer article.
 60. The method of claim 46, further comprising positioning an intermediate film layer between the first film layer and the nonwoven substrate.
 61. The method of claim 60, wherein the intermediate film layer comprises a third polymer comprising a polyolefin grafted with an anhydride, an acid, or an acrylate selected to improve adhesion to the nonwoven substrate; wherein the third polymer is the same or different than the first polymer.
 62. The method of claim 46, wherein the nonwoven substrate comprises randomly disposed continuous polymeric fibers, at least some of the fibers being bonded to one another.
 63. The method of claim 46, wherein the first film comprises a first weight ratio between the first polymer to the polar compound comprising from about 5.6:1 to about 4:1, and wherein a sum of the first polymer, the second polymer, and the polar compound comprises from about 50 to 55% by weight of the film layer.
 64. The method of claim 46, wherein the multilayer article has a moisture vapor transmission rate of at least about 8.5 perms, an adhesion strength between the nonwoven substrate and the first film is at least about 200 gram-force/in, or both.
 65. A method of forming a multilayer article, comprising: extrusion coating a monolithic film onto a spunbond nonwoven; wherein the monolithic film comprises (i) a first polymer comprising from about 5% by weight to 12% by weight of the monolithic film, the first polymer comprises a polyolefin grafted with an anhydride, an acid, or an acrylate; (ii) a second polymer comprising from 30% by weight to 35% by weight of the monolithic film, the second polymer comprising a polyether amide block copolymer that is capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids, and (iii) from at least about 1% by weight to at most about 3% by weight of a polyetheramine. 